JP2023128213A - electrostatic chuck device - Google Patents

Abstract

To provide an electrostatic chuck device having convex portions with excellent plasma resistance and high adhesion.SOLUTION: The electrostatic chuck device includes a base 11, a first adhesive layer 110, a first insulating organic film 120, an electrode 12, a second adhesive layer 130, a second insulating organic film 210, and a plurality of convex portions 14 on an attraction surface. The convex portions 14 have a ceramic layer 15 containing a ceramic film 16 and a resin binder. The ceramic film 16 contains ceramic particles 21 and a metal oxide 22. At least a portion of the ceramic particles 21 are bonded to each other via the metal oxide 22.SELECTED DRAWING: Figure 4

Description

The present invention relates to an electrostatic chuck device.

When manufacturing semiconductor integrated circuits using semiconductor wafers, or when manufacturing liquid crystal panels using insulating substrates such as glass substrates and films, it is necessary to use base materials such as semiconductor wafers, glass substrates, and insulating substrates. It is necessary to adsorb and hold it at a predetermined location. Therefore, in order to attract and hold these base materials, mechanical chucks, vacuum chucks, and the like have been used. However, these holding methods have problems such as difficulty in holding the substrate (object to be adsorbed) uniformly, inability to use in vacuum, and excessive rise in temperature on the surface of the substrate. . Therefore, in recent years, electrostatic chuck devices that can solve these problems have been used to hold objects to be attracted.

An electrostatic chuck device mainly includes a conductive support member serving as an internal electrode and a dielectric layer made of a dielectric material covering the conductive support member. This main portion allows an object to be adsorbed to be adsorbed. When a voltage is applied to the internal electrodes in the electrostatic chuck device to create a potential difference between the object to be attracted and the conductive support member (internal electrode), electrostatic adsorption force is generated in the dielectric layer. Thereby, the object to be attracted is supported substantially flatly with respect to the conductive support member. In addition, by forming a plurality of uneven parts on the adsorption surface of the electrostatic chuck device and adsorbing the object to the surface formed by the upper surface of the plurality of protrusions, fine particles can be applied to the adsorption surface of the dielectric layer by thermal spraying. When forming roughness, particles are prevented from adhering to the adsorbed object.

Conventionally, it has been known to partially shave off the surface of a ceramic dielectric layer, which will serve as an attraction surface, to perform dimple processing to form a large number of unevenness (see, for example, Patent Document 1). In Patent Document 1, the outer peripheral part of the surface with a width of 8 mm and a plurality of regularly arranged circular parts with a diameter of 4 mm are masked, and the remaining part is blasted to remove a depth of 20 μm to provide a step. This prevents particles from adhering to the suction surface during thermal spraying of ceramics.

The number of particles on the back surface of the silicon wafer increases as the contact area between the silicon wafer and the electrostatic chuck device increases. Therefore, in order to reduce the contact area between the silicon wafer and the electrostatic chuck device, it is known to form a plurality of uneven portions on the suction surface of the electrostatic chuck device (for example, see Patent Document 2). In Patent Document 2, after masking the suction surface with a predetermined pattern, blasting is performed to form a plurality of uneven portions.

It is also known that after masking the surface of a member to be treated (adsorbed object) with a masking material having openings in a predetermined pattern shape, a thermal spray material is sprayed through the masking material to pattern a thermal sprayed film. (For example, see Patent Document 3).

JP2003-264223A Japanese Patent Application Publication No. 2007-201068 JP 2017-177029 Publication

As described in Patent Documents 1 to 3, when a thermal spray film having fine irregularities is formed on the adsorption surface of an electrostatic chuck device by thermal spraying, the following problems occur.
Ceramic particles that can be used for thermal spraying are limited to relatively large particles with an average primary particle diameter of several tens of μm or more. Therefore, the irregularities formed by thermal spraying have many voids, have poor plasma resistance, and have poor adhesion to the base.
When forming irregularities by thermal spraying, it is necessary to stack ceramic particles in multiple layers, which poses a problem in that it takes time. Since the film thickness that can be created by one thermal spraying process is 2 μm to 3 μm, in order to form a convex portion with a height of 30 μm, thermal spraying must be performed approximately 20 times, which was inefficient. Note that since the surface of the sprayed film is polished after formation, it is necessary to form the sprayed film thicker than the intended thickness.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an electrostatic chuck device having a convex portion with excellent plasma resistance and high adhesion.

The present invention has the following aspects.
[1] An electrostatic chuck device having a plurality of convex portions on an adsorption surface, wherein the convex portion has a ceramic film and a ceramic layer containing a resin binder, and the ceramic film has ceramic particles and a ceramic layer containing a resin binder. A metal oxide, and at least a portion of the ceramic particles are bonded to each other via the metal oxide.
[2] The electrostatic chuck device according to [1], wherein the ceramic particles are at least one selected from the group consisting of alumina, magnesia, yttria, zirconia, silica, and zinc oxide.
[3] The electrostatic chuck device according to [1] or [2], wherein the average primary particle diameter of the ceramic particles is 0.1 μm or less and 50 μm or less.
[4] The metal oxide is a metal oxide obtained by heat-treating the organometallic compound to decompose and remove organic components and oxidizing the metal constituting the organometallic compound. The electrostatic chuck device according to any one of [1] to [3].
[5] The electrostatic chuck device according to [4], wherein the metal constituting the organometallic compound is at least one selected from the group consisting of aluminum, yttrium, and magnesium.

According to the present invention, it is possible to provide an electrostatic chuck device having a convex portion with excellent plasma resistance and high adhesion.

1 is a schematic cross-sectional view showing an electrostatic chuck device according to an embodiment of the present invention. FIG. 2 is a schematic cross-sectional view showing a convex portion constituting an electrostatic chuck device according to an embodiment of the present invention. 1 is a schematic cross-sectional view showing an electrostatic chuck device according to an embodiment of the present invention. 1 is a schematic cross-sectional view showing an electrostatic chuck device according to an embodiment of the present invention. FIG. 3 is a schematic plan view showing a mask sheet for forming convex portions.

Hereinafter, embodiments of an electrostatic chuck device according to the present invention will be described with reference to the drawings. Note that the drawings used in the following description show characteristic parts enlarged for convenience, and the dimensional ratio of each component may differ from the actual one. Further, the materials, dimensions, etc. exemplified in the following description are merely examples, and the present invention is not limited thereto, and may be modified as appropriate without changing the gist thereof.

[Electrostatic chuck device]
An electrostatic chuck device according to an embodiment of the present invention is an electrostatic chuck device having a plurality of convex portions on a suction surface, wherein the convex portions include a ceramic film and a ceramic layer containing a resin binder. The ceramic film contains ceramic particles and a metal oxide, and at least some of the ceramic particles are bound together via the metal oxide.

An electrostatic chuck device according to an embodiment of the present invention will be described with reference to FIGS. 1 and 2.
FIG. 1 is a schematic cross-sectional view showing an electrostatic chuck device according to this embodiment. FIG. 2 is a schematic cross-sectional view showing a convex portion constituting the electrostatic chuck device according to the present embodiment.
The electrostatic chuck device 10 of this embodiment shown in FIG. 1 includes a base 11, an electrode 12, a ceramic layer 13, and a convex portion 14. The electrode 12 is formed on one surface (upper surface) 11a of the base 11. The ceramic layer 13 is formed on one surface 11a of the base 11 so as to cover the electrode 12, that is, to cover one surface (upper surface) 12a and side surface 12b of the electrode 12. The convex portion 14 is formed on one surface (upper surface) 13a of the ceramic layer 13.
Further, the convex portion 14 includes a ceramic layer 15 and a ceramic film 16. Ceramic layer 15 is formed on one surface 13a of ceramic layer 13, and ceramic film 16 is formed to cover one surface (top surface) 15a and side surface 15b of ceramic layer 15.
One surface (upper surface, front surface) 16a of the convex portion 14 is an attraction surface of the electrostatic chuck device 10.

<Base 11>
Although the base 11 is not particularly limited, examples thereof include a ceramic base, a silicon carbide base, and a metal base made of aluminum, stainless steel, or the like.

<Electrode 12>
The electrode 12 is not particularly limited as long as it is made of a conductive material that can exhibit electrostatic attraction when a voltage is applied. As the electrode 12, for example, a thin film made of a metal such as copper, aluminum, gold, silver, platinum, chromium, nickel, or tungsten, or a thin film made of at least two metals selected from the above metal group is preferably used. It will be done. Examples of such metal thin films include those formed by vapor deposition, plating, sputtering, etc., and those formed by applying and drying a conductive paste. A specific example of the electrode 12 is a metal foil such as copper foil.

The electrode 12 may be a monopolar structure made of a single layer, or a bipolar structure divided into two or more parts. The electrode pattern and shape of the electrode 12 are not particularly limited. The arrangement of the electrodes 12 can be designed as appropriate.

The thickness of the electrode 12 is not particularly limited. The thickness of the electrode 12 is preferably 1 μm or more and 100 μm or less, more preferably 3 μm or more and 20 μm or less. When the thickness of the electrode 12 is equal to or greater than the lower limit value, when the ceramic layer 13 is formed to cover the electrode 12, unevenness is less likely to occur on one surface (upper surface) 12a of the electrode 12. When the thickness of the electrode 12 is less than or equal to the upper limit value, sufficient bonding strength between the electrode 12 and other layers can be obtained.

<Ceramic layer 13>
The ceramic layer 13 is composed of a ceramic sintered body or a ceramic sprayed body.
The materials constituting the ceramic sintered body and the ceramic sprayed body are not particularly limited, and include, for example, boron nitride, aluminum nitride, zirconium oxide, silicon oxide, tin oxide, indium oxide, quartz glass, soda glass, lead glass, and borium. Examples include silicate glass, zirconium nitride, and titanium oxide. These materials may be used alone or in combination of two or more.

The average primary particle diameter of the material constituting the ceramic sintered body and the ceramic sprayed body is preferably 1 μm or more and 25 μm or less. When the average primary particle diameter of the material is within the above range, the voids in the ceramic sintered body and the ceramic sprayed body can be reduced, and the withstand voltage of the ceramic sintered body and the ceramic sprayed body can be improved.

The average primary particle size of the materials constituting the ceramic sintered body and the ceramic sprayed body can be measured by laser diffraction, scattering method, or the like.

The thickness of the ceramic layer 13 is preferably 5 μm or more and 200 μm or less, more preferably 10 μm or more and 100 μm or less. If the thickness of the ceramic layer 13 is less than 5 μm, sufficient plasma resistance cannot be obtained. When the thickness of the ceramic layer 13 exceeds 200 μm, thermal conductivity decreases.

<Convex portion 14>
Ceramic layer 15 contains ceramic particles and a resin binder.
As the ceramic particles constituting the ceramic layer 15, ceramic particles having the shape and material mentioned for the ceramic layer 13 can be used.
Since the ceramic layer 15 is a resin layer containing ceramic particles and a resin binder, it is possible to obtain an electrostatic chuck device with high adhesiveness and high withstand voltage due to the included resin binder.

The average primary particle size of the ceramic particles constituting the ceramic layer 15 is preferably 0.1 μm or more and 50 μm or less, more preferably 0.1 μm or more and 10 μm or less, and preferably 0.1 μm or more and 1 μm or less. More preferred. When the average primary particle size of the ceramic particles is within the above range, it becomes possible to form a film using small-sized particles, and the ceramic particles become closer together, resulting in an electrostatic chuck with high adhesion and good thermal conductivity. You can get the equipment.
The average primary particle diameter of the ceramic particles constituting the ceramic layer 15 can be measured by a laser diffraction/scattering method.

Examples of the resin binder in the ceramic layer 15 include epoxy resin, phenol resin, styrene block copolymer, polyamide resin, polyacrylamide resin, acrylic resin, acrylonitrile-butadiene copolymer, polyester resin, polyimide resin, silicone resin, and amine. Examples include one or more resins selected from compounds, bismaleimide compounds, and the like.
The ceramic layer 15 may contain 100 to 10,000 parts by mass, preferably 300 to 4,000 parts by mass, and more preferably 500 to 2,000 parts by mass of ceramic particles based on 100 parts by mass of the resin binder. .

The thickness of the ceramic layer 15 is not particularly limited. The thickness of the ceramic layer 15 is preferably 5 μm or more and 200 μm or less, more preferably 10 μm or more and 100 μm or less. When the thickness of the ceramic layer 15 is greater than or equal to the lower limit, insulation can be ensured. When the thickness of the ceramic layer 15 is less than or equal to the upper limit value, sufficient adsorption force by the electrode 12 is generated.

The ceramic film 16 is made of a ceramic composition containing a plurality of ceramic particles 21 and a plurality of metal oxides 22 . In the electrostatic chuck device 10 of this embodiment, at least some of the ceramic particles 21 are bound together via the metal oxide 22. That is, as shown in FIG. 2, one ceramic particle 21 (21A) included in the ceramic film 16 is bonded to another ceramic particle 21 via the metal oxide 22. Further, one ceramic particle 21 (21C) included in the ceramic film 16 is bound to another ceramic particle 21 (21B) via a metal oxide 22 (22A). Further, one ceramic particle 21 (21B) included in the ceramic film 16 is bound to another ceramic particle 21 via a metal oxide 22 (22B). One ceramic particle 21 may be in contact with one or more metal oxides 22 and may be bonded to one or more other ceramic particles 21 via each metal oxide 22. Further, the ceramic particles 21 may be in contact with other ceramic particles 21.

The thickness of the ceramic film 16 (height based on one surface 15a of the ceramic layer 15) is preferably 1 μm or more and 80 μm or less, more preferably 5 μm or more and 50 μm or less. When the thickness of the ceramic film 16 is equal to or greater than the lower limit, sufficient plasma resistance and voltage resistance are exhibited. When the thickness of the ceramic film 16 is less than or equal to the upper limit value, sufficient adsorption force is generated.

The arithmetic mean roughness (Ra) of the surface (upper surface) 16a of the ceramic film 16 is preferably 0.05 μm or more and 0.5 μm or less. When the arithmetic mean roughness (Ra) of the surface 16a of the ceramic film 16 is within the above range, the object to be adsorbed can be satisfactorily adsorbed. As the arithmetic mean roughness (Ra) of the surface 16a of the ceramic film 16 increases, the contact area between the adsorbed object and the ceramic film 16 decreases, and therefore the adsorption force also decreases.

The arithmetic mean roughness (Ra) of the surface 16a of the ceramic film 16 can be measured according to the method specified in JIS B0601-1994.

The content ratio of the ceramic particles 21 and the metal oxide 22 in the ceramic film 16 is preferably 80:20 to 98:2, and 90:10 to 96 in terms of mass. :4 is more preferable. When the content ratio of the ceramic particles 21 and the metal oxide 22 is within the above range, the metal oxide 22 can bond the ceramic particles 21 well.

<Ceramic particles 21>
The ceramic particles 21 are not particularly limited.
Examples of the shape of the ceramic particles 21 include spherical, true spherical, amorphous, acicular, fibrous, and plate-like shapes. Ceramic particles 21 having these shapes may be used alone or in combination of two or more.

Examples of the material of the ceramic particles 21 include ceramic particles mainly composed of oxide ceramics, non-oxide ceramics, and composite ceramics thereof.

Examples of oxide ceramics include alumina (aluminum oxide, Al ₂ O ₃ ), zirconia (zirconium oxide, ZrO ₂ ), yttria (yttrium oxide, Y ₂ O ₃ ), and talc (hydrated magnesium silicate, Mg ₃ Si _{4 )} . O ₁₀ (OH) ₁₀ ), hematite (iron (III) oxide, Fe ₂ O ₃ ), chromia (chromium (III) oxide, Cr ₂ O ₃ ), titania (titanium (IV) oxide, Ti ₂ O), magnesia (magnesium oxide, MgO), silica (silicon dioxide, SiO ₂ ), calcia (calcium oxide, CaO), ceria (cerium (IV) oxide, CeO ₂ ), tin oxide (SnO ₂ ), zinc oxide (ZnO), stair tight (magnesium metasilicate, MgO・SiO ₂ ), cordierite (2MgO・2Al ₂ O ₃・5SiO ₂ ), mullite (3Al ₂ O ₃・2SiO ₂ ), ferrite (MnFe ₂ O ₄ ), spinel (MgAl ₂ O ₄ ), zircon (ZrSiO ₄ ), barium titanate (BaTiO ₃ ), lead titanate (PbTiO ₃ ), forsterite (Mg ₂ SiO ₄ ), phosphorus-doped tin oxide (PTO), antimony-doped tin oxide (ATO), Examples include tin-doped indium oxide (ITO).
One type of oxide ceramic may be used alone, or two or more types may be used in combination.

Examples of non-oxide ceramics include nitride ceramics, carbide ceramics, boride ceramics, silicide ceramics, and phosphoric acid compounds.
Examples of nitride ceramics include boron nitride (BN), titanium nitride (TiN), silicon nitride (Si ₃ N ₄ ), gallium nitride (GaN), aluminum nitride (AlN), carbon nitride (CN _x ), and sialon ( Si ₃ N ₄ -AlN-Al ₂ O ₃ solid solution) and the like.
Examples of carbide ceramics include tungsten carbide (WC), chromium carbide (CrC), vanadium carbide (VC), niobium carbide (NbC), molybdenum carbide (MoC), tantalum carbide (TaC), titanium carbide (TiC), Examples include zirconium carbide (ZrC), hafnium carbide (HfC), silicon carbide (SiC), and boron carbide (B ₄ C).
Examples of boride ceramics include molybdenum boride (MoB), chromium boride (CrB ₂ ), hafnium boride (HfB ₂ ), zirconium boride (ZrB ₂ ), tantalum boride (TaB ₂ ), and boride. Examples include titanium (TiB ₂ ).
Examples of the silicide ceramics include zirconium silicate oxide, hafnium silicate oxide, titanium silicate oxide, lanthanum silicate, yttrium silicate oxide, titanium silicate, tantalum silicate oxide, and tantalum oxynitride silicate.
Examples of the phosphoric acid compound include hydroxyapatite, calcium phosphate, and the like.
One type of non-oxide ceramics may be used alone, or two or more types may be used in combination.

The ceramic particles 21 are preferably at least one selected from the group consisting of alumina, magnesia, yttria, zirconia, silica, and zinc oxide. When the ceramic particles 21 are made of at least one compound selected from the above group, plasma resistance is improved.

The average primary particle diameter of the ceramic particles 21 is preferably 0.1 μm or more and 50 μm or less, more preferably 0.1 μm or more and 10 μm or less, and even more preferably 0.1 μm or more and 1 μm or less. When the average primary particle diameter of the ceramic particles 21 is within the above range, the voids in the protrusions 14 are reduced and the withstand voltage of the protrusions 14 is improved.

The average primary particle diameter of the ceramic particles 21 can be measured by a laser diffraction/scattering method.

The content of the ceramic particles 21 in the ceramic film 16 is preferably 80% by mass or more and 98% by mass or less, more preferably 90% by mass or more and 96% by mass or less, based on 100% by mass of the total mass of the ceramic film 16. preferable. If the content of the ceramic particles 21 is less than the lower limit, the viscosity becomes too low and dot formation by mask printing tends to become difficult. When the content of the ceramic particles 21 exceeds the upper limit, it is difficult to bond the ceramic particles 21 together, and chipping is likely to occur.

<Metal oxide 22>
The metal oxide 22 is a metal oxide obtained by heat-treating a metal organic compound to decompose and remove organic components and oxidizing the metal constituting the metal organic compound.
Examples of the metal oxide 22 include gold, silver, platinum, palladium, iridium, rhodium, ruthenium, lead, bismuth, silicon, chromium, cobalt, nickel, iron, boron, antimony, cadmium, vanadium, aluminum, calcium, and magnesium. , manganese, zinc, zirconium, barium, strontium, yttrium, lanthanum, and other oxides.
Specific examples of the metal oxide 22 include aluminum oxide, yttrium oxide, magnesium oxide, nickel oxide, zinc oxide, and the like.
One type of metal oxide 22 may be used alone, or two or more types may be used in combination.

The metal oxide 22 is preferably at least one selected from the group consisting of aluminum oxide, yttrium oxide, and magnesium oxide. That is, the metal oxide 22 is preferably alumina (aluminum oxide, Al ₂ O ₃ ), yttria (yttrium oxide, Y ₂ O ₃ ), or magnesia (magnesium oxide, MgO). Plasma resistance is further improved when the metal oxide 22 is yttria (yttrium oxide, Y ₂ O ₃ ) or magnesia (magnesium oxide, MgO).

The content of the metal oxide 22 in the ceramic film 16 is preferably 2% by mass or more and 20% by mass or less, and preferably 4% by mass or more and 10% by mass or less, based on 100% by mass of the total mass of the ceramic film 16. More preferred. If the content of the metal oxide 22 is less than the lower limit, the ceramic particles 21 will not be bound together, making it difficult to ensure the strength of the convex portions. When the content of metal oxide 22 exceeds the upper limit, it is likely to be difficult to form dots.

The ceramic film 16 may contain components other than the ceramic particles 21 and the metal oxide 22. Components other than the ceramic particles 21 and the metal oxide 22 include, for example, resin. Including resin improves the strength of the convex portions and improves the withstand voltage.

According to the electrostatic chuck device 10 of this embodiment, it is possible to provide an electrostatic chuck device that has excellent plasma resistance and high mechanical strength.

[Manufacturing method of electrostatic chuck device]
Hereinafter, with reference to FIG. 1, a method for manufacturing the electrostatic chuck device of this embodiment will be described.

"Paint preparation process (paint preparation process)"
The method for manufacturing an electrostatic chuck device of this embodiment may include a paint preparation step of preparing a paint containing ceramic particles and metal resinate.
As the ceramic particles, those mentioned above are used.

The content of ceramic particles in the paint is preferably 20% by mass or more and 80% by mass or less, more preferably 40% by mass or more and 70% by mass or less, based on 100% by mass of the total mass of the paint. If the content of ceramic particles is less than the lower limit, the strength of the convex portions will be low, and the convex portions will be likely to chip, resulting in generation of particles. When the content of ceramic particles exceeds the above upper limit, the viscosity of the coating material becomes high and coating tends to become difficult.

The content of metal resinate in the paint is preferably 20% by mass or more and 80% by mass or less, more preferably 30% by mass or more and 60% by mass or less, based on 100% by mass of the total mass of the paint. If the content of the metal resinate is less than the lower limit, the viscosity of the paint becomes high and coating becomes difficult. When the content of metal resinate exceeds the above upper limit, bulk is generated in the convex portions and the strength is reduced. This tends to cause chipping of the convex portions, which causes particles to be generated.

The content ratio of ceramic particles and metal resinate in the paint is preferably ceramic particles: metal resinate in a mass ratio of 2:8 to 8:2, more preferably 4:6 to 6:4. . When the content ratio of the ceramic particles and the metal resinate is within the above range, the metal oxide can bond between the ceramic particles.

<Metal resinate>
Metal resinates are liquids or pastes containing organometallic compounds. Metal resinates are heat-treated to remove organic components through oxidative decomposition and oxidize metals constituting the organometallic compound, thereby producing highly pure metal oxides. The obtained metal oxide forms an extremely thin metal film. By using metal resinate, for example, a metal film having a thickness of about 0.1 μm or more and 0.6 μm or less can be obtained. This metal film binds at least some of the ceramic particles to form a ceramic film.

Metal resinates are synthesized by reacting the following metal components such as halides, nitrates, acetates, or oxides with carboxylic acids, polynuclear fatty acids such as abietic acid, or gum rosin whose main component is abietic acid. . As the carboxylic acid, aliphatic carboxylic acid, cycloaliphatic carboxylic acid, aromatic carboxylic acid, etc. are used.

Examples of metal components include gold, silver, platinum, palladium, iridium, rhodium, ruthenium, lead, bismuth, silicon, chromium, cobalt, nickel, iron, boron, antimony, cadmium, vanadium, aluminum, calcium, magnesium, and manganese. , zinc, zirconium, barium, strontium, yttrium, lanthanum, etc.
One type of metal component may be used alone, or two or more types may be used in combination.

<Solvent>
It is preferable to mix a solvent with the above paint. Examples of the solvent include alcohols, ketones, esters, hydrocarbons, and ethers.
Examples of alcohols include methanol, ethanol, propanol, butanol, and the like.
Examples of ketones include methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.
Examples of esters include ethyl acetate, propyl acetate, butyl acetate, and the like.
Examples of hydrocarbons include toluene and xylene.
Examples of the ethers include methyl cellosolve, ethyl cellosolve, butyl cellosolve, and tetrahydrofuran.

<Other ingredients>
The above paint may contain components other than the ceramic particles, metal resinate, and solvent. Components other than the ceramic particles, metal resinate, and solvent include, for example, dispersants, surfactants, and the like.

Examples of methods for preparing the paint include a method of stirring and mixing ceramic particles, metal resinate, and a solvent. As a mixing method, for example, a mixing method using a stirrer such as a rotation-revolution type stirrer, a homogenizer, a high-pressure jet mill, or an ultrasonic stirrer is used.

"Process of forming electrodes (electrode formation process)"
The method for manufacturing the electrostatic chuck device of this embodiment may include an electrode forming step of forming the electrode 12 on one surface (upper surface) 11a of the base 11.
In the electrode forming step, a metal such as copper is deposited on one surface 11a of the base 11 to form a metal thin film (metal thin film). Thereafter, etching is performed to pattern the thin metal film into a predetermined shape, thereby forming the electrode 12.

"Step of forming ceramic layer 13 (ceramic layer 13 forming step)"
The method for manufacturing an electrostatic chuck device of this embodiment may include a ceramic layer 13 forming step of forming a ceramic layer 13 on one surface (upper surface) 11a of the base 11 so as to cover the electrode 12. good.

When the ceramic layer 13 is a ceramic sintered body, first, an adhesive is applied on one surface (upper surface) 11a of the base 11 so as to cover the electrode 12 to form an adhesive layer (not shown). .
Next, a ceramic sintered body is laminated on one surface (upper surface) 11a of the base 11 via an adhesive layer so as to cover the electrode 12.

When the ceramic layer 13 is a ceramic sprayed body, the above-mentioned material is sprayed onto one surface (upper surface) 11a of the base 11 so as to cover the electrode 12 to form the ceramic sprayed body. As a method for forming a ceramic sprayed body by thermal spraying, a plasma spraying method or the like is used.

"Step of forming ceramic layer 15 (ceramic layer 15 forming step)"
In the ceramic layer 15 forming step, a masking sheet having a predetermined shape of convex portions 14 is placed on one surface (upper surface) 13a of the ceramic layer 13, and ceramic particles containing a resin binder are applied to form the ceramic layer 15. . Thereafter, the masking sheet is removed, and the ceramic layer 15 in the shape of the convex portions 14 can be obtained by heating and drying and curing.
Since the ceramic layer 15 can be formed by coating, it is possible to produce a thick film, and it can be produced by one coating, which can shorten the production time compared to the ceramic spraying method or the ceramic sintering method.

Coating methods for the above slurry include, for example, coating methods using coating equipment such as spray, gravure coater, roll coater, blade coater, air knife coater, and rod coater, dip coating, offset printing, and screen printing. Printing methods such as the following are used.

The thickness of the coating film of the slurry is preferably 1 μm or more and 200 μm or less, more preferably 10 μm or more and 50 μm or less. When the thickness of the coating film is equal to or greater than the lower limit, the ceramic layer obtained through the heating step exhibits sufficient plasma resistance and voltage resistance. When the thickness of the coating film is below the upper limit value, the ceramic layer obtained through the heating process will generate sufficient adsorption force.

Examples of the heating method for the slurry coating include a thermal method, plasma heating, an infrared method, and a lamp method. The heating temperature and heating time for the slurry coating film are, for example, as follows. The coated film is dried by heating at 100° C. or higher and 150° C. or lower for 1 minute or more and 10 minutes or less to remove the solvent contained in the coated film. Thereafter, the ceramic layer 15 is obtained by heating the coating film at 100° C. or more and 300° C. or less for 30 minutes or more and 2 hours or less.

"Coating process of ceramic film 16"
In the coating process of the ceramic film 16, the above paint is applied to one surface (top surface) 15a and the other surface (side surface) 15b of the ceramic layer 15 to form a coating film. Specifically, one surface (top surface) 15a of the ceramic layer 15, the other surface (side surface) 15b of the ceramic layer 15, and one surface (top surface) 13a of the ceramic layer 13 are coated.

Examples of coating methods include coating methods using coating equipment such as spray, gravure coater, roll coater, blade coater, air knife coater, and rod coater, dip coating, offset printing, screen printing, etc. The following printing methods are used.

The thickness of the coating film is preferably 1 μm or more and 80 μm or less, more preferably 5 μm or more and 50 μm or less. When the thickness of the coating film is equal to or greater than the lower limit, the ceramic film obtained through the heating step exhibits sufficient plasma resistance and voltage resistance. When the thickness of the coating film is less than or equal to the upper limit value, the ceramic film obtained through the heating process will generate sufficient adsorption force.

"Heating process"
In the heating step, the coating film formed on the ceramic layer 15 in the coating step is heated. As a result, a ceramic film 16 containing the above-mentioned ceramic particles and metal oxide is formed on one surface (upper surface) 15a of the ceramic layer 15.

Examples of heating methods for the coating film include thermal methods, plasma heating, infrared rays, and lamp methods. By adding ultraviolet irradiation to these heating methods, organic components can be removed at lower temperatures and a metal oxide film can be obtained.

The heating temperature and heating time of the coating film are, for example, as follows. The coated film is dried by heating at 100° C. or higher and 150° C. or lower for 1 minute or more and 10 minutes or less to remove the solvent contained in the coated film. Thereafter, a ceramic film is obtained by heating the coating film at a temperature of 500° C. or more and 700° C. or less for 30 minutes or more and 2 hours or less. Heat treatment can also be performed at a lower temperature (400° C. or lower) by making the organic matter in the resinate easily decomposable by irradiation with ultraviolet rays.

Further, the method for manufacturing an electrostatic chuck device of this embodiment may include a polishing step of polishing the surface 16a of the convex portion obtained through the heating step.
By polishing the surface 16a of the convex portion 14 to within the range of the arithmetic mean roughness (Ra) described above, the adsorption force of the ceramic film can be improved.

According to the method for manufacturing a ceramic film of the present embodiment, it is possible to provide an electrostatic chuck device having a convex portion with excellent plasma resistance and high adhesion.

<Other embodiments>
Note that the present invention is not limited to the above embodiments.

For example, an electrostatic chuck device 100 according to a first modification as shown in FIG. 3 and an electrostatic chuck device 200 according to a second modification as shown in FIG. 4 may be employed. In the electrostatic chuck devices 100 and 200 according to the modified example, the same components as those in the embodiment described above are given the same reference numerals, and the explanation thereof will be omitted, and only the different points will be explained.

[First modification]
An electrostatic chuck device 100 according to a first modification example shown in FIG. It includes an organic film 120 and a second adhesive layer 130. The first insulating organic film 120 is attached to one surface (upper surface) 11a of the base 11 via the first adhesive layer 110. The electrode 12 is formed on one surface (upper surface) 120a of the first insulating organic film 120. The ceramic layer 13 is formed on one surface (upper surface) 120a of the first insulating organic film 120 so as to cover the electrode 12, that is, to cover one surface (upper surface) 12a and side surfaces 12b of the electrode 12. It is formed on the electrode 12 via the formed second adhesive layer 130. The convex portion 14 is formed on one surface (upper surface) 13a of the ceramic layer 13.

<Adhesive layer>
Examples of the adhesive constituting the first adhesive layer 110 and the second adhesive layer 130 include epoxy resin, phenol resin, styrene block copolymer, polyamide resin, acrylonitrile-butadiene copolymer, polyester resin, and polyimide. Examples include adhesives containing at least one resin as a main component selected from the group consisting of resins, silicone resins, amine compounds, bismaleimide compounds, and the like.

Examples of the epoxy resin include bisphenol type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, trihydroxyphenylmethane type epoxy resin, Examples include difunctional or polyfunctional epoxy resins such as tetraglycidylphenolalkane epoxy resins, naphthalene epoxy resins, diglycidyl diphenylmethane epoxy resins, and diglycidyl biphenyl epoxy resins. Among these, bisphenol type epoxy resins are preferred. Among bisphenol type epoxy resins, bisphenol A type epoxy resins are particularly preferred. In addition, when using an epoxy resin as the main component, the adhesive may contain epoxy resin additives such as imidazoles, tertiary amines, phenols, dicyandiamides, aromatic diamines, and organic peroxides, as necessary. A curing agent or curing accelerator can also be blended.

Examples of the phenolic resin include alkylphenol resin, p-phenylphenol resin, novolak phenol resin such as bisphenol A type phenol resin, resol phenol resin, and polyphenyl paraphenol resin.

Examples of the styrene block copolymer include styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), and styrene-ethylene-propylene-styrene copolymer (SEPS). etc.

The thickness of the first adhesive layer 110 is not particularly limited. The thickness of the first adhesive layer 110 is preferably 1 μm or more and 100 μm or less, more preferably 5 μm or more and 20 μm or less. When the thickness of the first adhesive layer 110 is less than the lower limit, the withstand voltage tends to decrease. When the thickness of the first adhesive layer 110 exceeds the upper limit, heat conduction tends to be poor.

The thickness of the second adhesive layer 130 is not particularly limited. The thickness of the second adhesive layer 130 is preferably 5 μm or more and 200 μm or less, more preferably 10 μm or more and 50 μm or less. When the thickness of the first adhesive layer 110 is less than the lower limit, the withstand voltage tends to decrease. When the thickness of the second adhesive layer 130 exceeds the upper limit, heat conduction tends to deteriorate.
The first adhesive layer 110 and the second adhesive layer 130 may have the same material and thickness, or may have different materials.

<First insulating organic film 120>
The material constituting the first insulating organic film 120 is not particularly limited, and includes, for example, polyesters such as polyethylene terephthalate, polyolefins such as polyethylene, polyimide, polyamide, polyamideimide, polyether sulfone, polyphenylene sulfide, Examples include polyetherketone, polyetherimide, triacetylcellulose, silicone rubber, polytetrafluoroethylene, and the like. Among these, polyesters, polyolefins, polyimides, silicone rubber, polyetherimide, polyethersulfone, and polytetrafluoroethylene are preferred, and polyimide is more preferred, since they have excellent insulation properties. As the polyimide film, for example, Kapton (trade name) manufactured by DuPont-Toray Co., Ltd., Upilex (trade name) manufactured by Ube Industries, Ltd., etc. are used.

The thickness of the first insulating organic film 120 is not particularly limited. The thickness of the first insulating organic film 120 is preferably 10 μm or more and 100 μm or less, more preferably 25 μm or more and 50 μm or less. When the thickness of the first insulating organic film 120 is equal to or greater than the lower limit, insulation can be ensured. When the thickness of the first insulating organic film 120 is less than or equal to the upper limit value, sufficient adsorption force by the electrode 12 is generated.

According to the electrostatic chuck device 100 of the first modification, it is possible to provide an electrostatic chuck device that has a convex portion that is excellent in plasma resistance and has high adhesiveness.

[Method for manufacturing electrostatic chuck device of first modification]
The method for manufacturing the electrostatic chuck device of the first modification includes the step of laminating a first insulating organic film 120 on one surface (upper surface) of the base 11 via the first adhesive layer 110 (hereinafter referred to as , "Insulating organic film 120 lamination step"), a step of forming the electrode 12 on one surface (upper surface) of the first insulating organic film 120 (electrode formation step), and one surface of the electrode 12 ( a step (ceramic layer 13 formation step) of forming a ceramic layer 13 on one surface (top surface) of the ceramic layer 13 via a second adhesive layer 130; a step (ceramic layer 15 formation step), a step of applying the above paint to form a coated film (ceramic film 16 coating step), and a step of heating the coated film (heating step).
Hereinafter, with reference to FIG. 3, a method for manufacturing the electrostatic chuck device of the first modification will be described.

"Paint preparation process"
The method for manufacturing an electrostatic chuck device of this embodiment may include a paint preparation step of preparing a paint containing ceramic particles and metal resinate, similar to the method for manufacturing an electrostatic chuck device of the above-described embodiments. good.
As the paint, the same paint as in the manufacturing method of the electrostatic chuck device of the above-described embodiment is used.

"Insulating organic film 120 lamination process"
In the step of laminating the insulating organic film 120, first, the above adhesive is applied to one surface (upper surface) 11a of the base 11 to form the first adhesive layer 110.

Examples of the method for applying the adhesive to one surface (upper surface) 11a of the base 11 include a method using a coating device such as a gravure coater, a roll coater, a blade coater, an air knife coater, and a rod coater; Printing methods such as offset printing and screen printing are used.

Next, a first insulating organic film 120 is laminated on one surface (upper surface) 11a of the base 11 via the first adhesive layer 110.
Thereafter, the laminate including the base 11, the first adhesive layer 110, and the first insulating organic film 120 is heated at a predetermined temperature for a predetermined period of time, or is left at room temperature for a predetermined period of time. The adhesive layer 110 is cured.

"Electrode formation process"
In the electrode forming step, the electrostatic chuck device manufacturing method of the above-described embodiment is applied to one surface (top surface) 120a of the first insulating organic film 120 laminated on one surface (top surface) 11a of the base 11. Similarly, a metal thin film (metal thin film) is formed. Thereafter, etching is performed to pattern the thin metal film into a predetermined shape, thereby forming the electrode 12.

"Ceramic layer 13 formation process"
In the ceramic layer 13 forming step, first, on one surface (upper surface) 120a of the first insulating organic film 120, so as to cover the electrode 12, that is, one surface (upper surface) 12a and side surface 12b of the electrode 12. The second adhesive layer 130 is formed by applying the above-mentioned adhesive so as to cover the second adhesive layer 130 .

As a method for applying the adhesive to one surface (upper surface) 120a of the first insulating organic film 120 and the electrode 12, a method similar to that for forming the first adhesive layer 110 described above is used.

Next, the ceramic layer 13 is laminated on one surface (upper surface) 120a of the first insulating organic film 120 via the second adhesive layer 130.
Thereafter, the laminate including the base 11, the first adhesive layer 110, the first insulating organic film 120, the electrode 12, the second adhesive layer 130, and the ceramic layer 13 is heated at a predetermined temperature for a predetermined time. , the second adhesive layer 130 is cured by leaving it at room temperature for a predetermined period of time.

"Ceramic layer 15 formation process"
In the ceramic layer 15 forming step, the ceramic layer 15 is formed on one surface (upper surface) 13a of the ceramic layer 13 in the same manner as in the manufacturing method of the electrostatic chuck device of the above-described embodiment.

"Coating process of ceramic film 16"
In the coating process of the ceramic film 16, one surface (top surface) 15a of the ceramic layer 15 and the other surface (side surface) of the ceramic layer 15 are coated in the same manner as in the manufacturing method of the electrostatic chuck device of the above-described embodiment. 15b and one surface (upper surface) 13a of the ceramic layer 13, the above paint is applied to form a coating film.

"Heating process"
In the heating step, one surface (upper surface) 15a of the ceramic layer 15 and the other surface (side surface) 15b of the ceramic layer 15 are coated in the coating step in the same manner as in the manufacturing method of the electrostatic chuck device of the above-described embodiment. The convex portions 14 are obtained by heating the coating film formed on one surface (upper surface) 13a of the ceramic layer 13.

Further, the method for manufacturing an electrostatic chuck device according to the present embodiment may include a polishing step of polishing the surface 16a of the convex portion 14, as in the method for manufacturing a ceramic film according to the above-described embodiment.

According to the method for manufacturing an electrostatic chuck device according to the first modification, it is possible to provide an electrostatic chuck device having a convex portion with excellent plasma resistance and high adhesion.

[Second modification]
An electrostatic chuck device 200 according to a second modification example shown in FIG. 4 includes a base 11, an electrode 12, a convex portion 14, a first adhesive layer 110, a first insulating organic film 120, A second adhesive layer 130 and a second insulating organic film 210 are provided. The first insulating organic film 120 is attached to one surface (upper surface) 11a of the base 11 via the first adhesive layer 110. The electrode 12 is formed on one surface (upper surface) 120a of the first insulating organic film 120. The second insulating organic film 210 is disposed on one surface (upper surface) 120a of the first insulating organic film 120 so as to cover the electrode 12, that is, on one surface (upper surface) 12a and side surfaces of the electrode 12. It is formed on the electrode 12 with a second adhesive layer 130 formed so as to cover the electrode 12b. The convex portion 14 is formed on one surface (upper surface) 210a of the second insulating organic film 210.

<Insulating organic film 210>
The second insulating organic film 210 can be the same as the first insulating organic film 120 in the electrostatic chuck device 100 of the first modification described above. The first insulating organic film 120 and the second insulating organic film 210 may have the same material and thickness, or may have different materials.

According to the electrostatic chuck device 200 of the second modification, it is possible to provide an electrostatic chuck device that has excellent plasma resistance and high mechanical strength.

[Method for manufacturing electrostatic chuck device of second modification]
The method for manufacturing the electrostatic chuck device of the second modification includes a step (electrode formation step) of forming the electrode 12 on one surface (upper surface) of the first insulating organic film 120, and a step of forming the electrode 12 on one surface (upper surface) of the first insulating organic film 120. A step of laminating a second insulating organic film 210 on one side (top surface) of the base 11 via a second adhesive layer 130 (referred to as an insulating organic film 210 lamination step); The step of laminating the first insulating organic film 120 via the first adhesive layer 110 (hereinafter referred to as the "insulating organic film 120 laminating step") and the step of laminating the first insulating organic film 120 via the first adhesive layer 110 (hereinafter referred to as "insulating organic film 120 laminating step") a step of forming a ceramic layer 15 on the upper surface (ceramic layer 15 forming step), a step of applying the above-mentioned paint to form a coated film (ceramic film 16 coating step), and a step of forming the coated film on the upper surface). It has a step of heating (heating step).
Hereinafter, with reference to FIG. 4, a method for manufacturing an electrostatic chuck device according to a second modification will be described.

"Paint preparation process"
The method for manufacturing an electrostatic chuck device of this embodiment may include a paint preparation step of preparing a paint containing ceramic particles and metal resinate, similar to the method for manufacturing an electrostatic chuck device of the above-described embodiments. good.
As the paint, the same paint as in the manufacturing method of the electrostatic chuck device of the above-described embodiment is used.

"Electrode formation process"
In the electrode forming step, a metal thin film (metal thin film) is formed on one surface (upper surface) 120a of the first insulating organic film 120 in the same manner as in the manufacturing method of the electrostatic chuck device of the above-described embodiment. . Thereafter, etching is performed to pattern the thin metal film into a predetermined shape, thereby forming the electrode 12.

"Insulating organic film 210 lamination process"
In the insulating organic film 210 lamination process, first, on one surface (upper surface) 120a of the first insulating organic film 120, so as to cover the electrode 12, that is, one surface (upper surface) 12a of the electrode 12 and The above adhesive is applied to form the second adhesive layer 130 so as to cover the side surface 12b.

As a method for applying the adhesive to one surface (upper surface) 120a of the first insulating organic film 120 and the electrode 12, a method similar to that for forming the first adhesive layer 110 described above is used.

Next, the second insulating organic film 210 is laminated on one surface (upper surface) 120a of the first insulating organic film 120 via the second adhesive layer 130.
Thereafter, the laminate including the first insulating organic film 120, the electrode 12, the second adhesive layer 130, and the second insulating organic film 210 is heated at a predetermined temperature for a predetermined time, or at room temperature for a predetermined time. By leaving it to stand, the second adhesive layer 130 is cured to obtain a laminate a.

"Insulating organic film 120 lamination process"
In the insulating organic film lamination step, the above film is applied to one surface (upper surface) 11a of the base 11 via the first adhesive layer 110 in the same manner as in the manufacturing method of the electrostatic chuck device of the above-described embodiment. The exposed first insulating organic film 120 surface of the obtained laminate a is laminated to obtain a laminate b. Thereafter, the first adhesive layer 110 is cured by heating the laminate b at a predetermined temperature for a predetermined time or by leaving it at room temperature for a predetermined time.
Note that the adhesive layer 110 and the adhesive layer 130 may be manufactured by applying an adhesive paint, or may be manufactured as an adhesive sheet.

"Ceramic layer 15 formation process"
In the ceramic layer 15 forming step, the ceramic layer 15 is formed on one surface (upper surface) 210a of the second insulating organic film 210 in the same manner as in the manufacturing method of the electrostatic chuck device of the above-described embodiment.

"Coating process of ceramic film 16"
In the coating process of the ceramic film 16, one surface (top surface) 15a of the ceramic layer 15 and the other surface (side surface) of the ceramic layer 15 are coated in the same manner as in the manufacturing method of the electrostatic chuck device of the above-described embodiment. 15b and one surface (upper surface) 210a of the second insulating organic film 210, the above paint is applied to form a coating film.

"Heating process"
In the heating step, one surface (upper surface) 15a of the ceramic layer 15 and the other surface (side surface) 15b of the ceramic layer 15 are coated in the coating step in the same manner as in the manufacturing method of the electrostatic chuck device of the above-described embodiment. The convex portion 14 is obtained by heating the coating film formed on one surface (upper surface) 210a of the second insulating organic film 210.

Further, the method for manufacturing an electrostatic chuck device according to the present embodiment may include a polishing step of polishing the surface 16a of the convex portion 14, as in the method for manufacturing a ceramic film according to the above-described embodiment.

According to the method for manufacturing an electrostatic chuck device according to the second modification, it is possible to provide an electrostatic chuck device having a convex portion with excellent plasma resistance and high adhesion.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

[Example 1]
“Preparation of paint for forming ceramic layer 15”
2000 parts by mass of alumina particles having an average primary particle diameter of 0.3 μm were mixed and dissolved in an appropriate amount of water to 100 parts by mass of polyacrylamide resin to obtain a paint for forming the ceramic layer 15.

“Preparation of paint for forming ceramic film 16”
4 parts by mass of a toluene solution of yttrium laurate (solid content 10% by mass) was added to 6 parts by mass of spherical alumina particles (manufactured by Denka, Al ₂ O ₃ ) with an average primary particle diameter of 0.3 μm, and the mixture was rotated and revolved. The mixture was mixed using a type stirrer (manufactured by Photo Chemical Co., Ltd., trade name: Kakuhunter) to obtain a paint for forming the ceramic film 16.

"Fabrication of electrostatic chuck device"
An electrostatic chuck device having the same configuration as the second modified example shown in FIG. 4 was manufactured.
As the first insulating organic film 120, one side of a 12 μm thick polyimide resin sheet was plated to form a 9 μm thick copper foil. After applying a photoresist to the surface of the copper foil, a development process was performed after pattern exposure, and unnecessary copper foil was removed by etching.
Thereafter, the photoresist was removed by washing the copper foil on the polyimide resin sheet, electrodes 12 were formed, and a laminate composed of the polyimide resin sheet and the copper foil was obtained. Note that this electrode 12 is a comb-shaped electrode having two comb-shaped electrodes in which conductive parts with a width of 5 mm and insulating parts with a width of 5 mm are arranged alternately.

An insulating adhesive sheet semi-cured by drying and heating is laminated as a second adhesive layer 130 (thickness 20 μm) on the surface of the above laminate on which the electrode 12 is formed, and then the insulating adhesive sheet A polyimide resin sheet having a thickness of 12 μm was bonded to the surface of the second insulating organic film 210 and bonded by heat treatment. The insulating adhesive sheet contained 27 parts by mass of bismaleimide resin, 3 parts by mass of diaminosiloxane, 20 parts by mass of resol phenol resin, 10 parts by mass of biphenyl epoxy resin, and 240 parts by mass of ethyl acrylate-butyl acrylate-acrylonitrile copolymer. , which was mixed and dissolved in an appropriate amount of tetrahydrofuran and molded into a sheet shape was used.

Next, a semi-cured insulating adhesive sheet similar to the above is applied as a first adhesive layer 110 to the surface of the polyimide resin sheet on which the electrodes 12 are formed, opposite to the surface on which the electrodes 12 are formed. were laminated, adhered to one side of a base 11 made of aluminum, and bonded by heat treatment.

Next, a mask sheet (heat-resistant non-woven fabric) 300 having a large number of through holes 310 as shown in FIG. The solvent was removed by drying at 100° C. for 10 minutes. Thereafter, the mask sheet was peeled off, and a plurality of convex ceramic layers 15 having a thickness of about 100 μm were formed on the polyimide resin sheet.
Next, the ceramic film-forming paint was spray-coated on the entire surface of the polyimide resin sheet having the convex ceramic layer 15, and the solvent was removed by drying in the atmosphere. Thereafter, heat treatment was performed at 500°C for 2 hours in a constant temperature bath, and the surface of the convex portion of the ceramic film was polished with a #200 nanodia polyimide polishing sheet to form a plurality of convex portions made of the ceramic film 16 with a thickness of about 40 μm. An electrostatic chuck device was obtained. After polishing the surface of the convex part with the nanodiamond polyimide polishing sheet in the electrostatic chuck device, the convex part did not have any chips or the like, indicating that the ceramic particles were firmly bound together through the metal oxide. It could be confirmed.

[Example 2]
As a paint for forming the ceramic film 16, a toluene solution of yttrium laurate (solid content: 10% by mass) was added to 4 parts by mass of spherical alumina particles (manufactured by Denka, Al ₂ O ₃ ) with an average primary particle diameter of 0.3 μm. An electrostatic chuck device of Example 2 was produced in the same manner as Example 1 except that 6 parts by mass of the electrostatic chuck was added. After polishing the surface of the convex part with the nanodiamond polyimide polishing sheet in the electrostatic chuck device, the convex part did not have any chips or the like, indicating that the ceramic particles were firmly bound together through the metal oxide. It could be confirmed.

[Example 3]
As a paint for forming the ceramic film 16, a toluene solution of yttrium laurate (solid content 10% by mass) was added to 2 parts by mass of spherical alumina particles (manufactured by Denka, Al ₂ O ₃ ) with an average primary particle diameter of 0.3 μm. An electrostatic chuck device of Example 3 was produced in the same manner as Example 1 except that 8 parts by mass of the electrostatic chuck device was used. After polishing the surface of the convex part with the nanodiamond polyimide polishing sheet in the electrostatic chuck device, the convex part did not have any chips or the like, indicating that the ceramic particles were firmly bound together through the metal oxide. It could be confirmed.

[Example 4]
As a paint for forming the ceramic film 16, a toluene solution of yttrium laurate (solid content 10% by mass) was added to 8 parts by mass of spherical alumina particles (manufactured by Denka, Al ₂ O ₃ ) with an average primary particle diameter of 0.3 μm. An electrostatic chuck device of Example 4 was produced in the same manner as Example 1 except that 2 parts by mass of the electrostatic chuck was added. After polishing the surface of the convex part with the nanodiamond polyimide polishing sheet in the electrostatic chuck device, the convex part did not have any chips or the like, indicating that the ceramic particles were firmly bound together through the metal oxide. It could be confirmed.

[Example 5]
As a paint for forming the ceramic film 16, a toluene solution of yttrium laurate (solid content: 10% by mass) was added to 6 parts by mass of spherical alumina particles (manufactured by Denka, Al ₂ O ₃ ) with an average primary particle diameter of 0.1 μm. An electrostatic chuck device of Example 5 was produced in the same manner as Example 1 except that 4 parts by mass of the electrostatic chuck was added. After polishing the surface of the convex part with the nanodiamond polyimide polishing sheet in the electrostatic chuck device, the convex part did not have any chips or the like, indicating that the ceramic particles were firmly bound together through the metal oxide. It could be confirmed.

[Example 6]
As a paint for forming the ceramic film 16, 4 parts by mass of a toluene solution of yttrium laurate (solid content 10% by mass) was added to 6 parts by mass of spherical alumina particles (manufactured by Denka, Al ₂ O ₃ ) with an average primary particle diameter of 50 μm. An electrostatic chuck device of Example 6 was produced in the same manner as in Example 1 except that the same amount of the compound was used. After polishing the surface of the convex part with the nanodiamond polyimide polishing sheet in the electrostatic chuck device, the convex part did not have any chips or the like, indicating that the ceramic particles were firmly bound together through the metal oxide. It could be confirmed.

[Example 7]
As a paint for forming the ceramic film 16, instead of 4 parts by mass of a toluene solution of yttrium laurate (solid content 10% by mass), 4 parts by mass of a toluene solution of magnesium stearate (solid content 10% by mass) was added. An electrostatic chuck device of Example 7 was produced in the same manner as Example 1 except that the following was used. After polishing the surface of the convex part with the nanodiamond polyimide polishing sheet in the electrostatic chuck device, the convex part did not have any chips or the like, indicating that the ceramic particles were firmly bound together through the metal oxide. It could be confirmed.

[Example 8]
As a paint for forming the ceramic film 16, instead of 4 parts by mass of a toluene solution of yttrium laurate (solid content 10% by mass), 4 parts by mass of a toluene solution of nickel stearate (solid content 10% by mass) was added. An electrostatic chuck device of Example 8 was produced in the same manner as Example 1 except that the following was used. After polishing the surface of the convex part with the nanodiamond polyimide polishing sheet in the electrostatic chuck device, the convex part did not have any chips or the like, indicating that the ceramic particles were firmly bound together through the metal oxide. It could be confirmed.

[Example 9]
As a paint for forming the ceramic film 16, 4 parts by mass of a toluene solution of yttrium laurate (solid content 10% by mass) was added to 6 parts by mass of spherical magnesia particles (manufactured by Denka, MgO) with an average primary particle diameter of 0.3 μm. An electrostatic chuck device of Example 9 was produced in the same manner as Example 1 except that the additives were used. After polishing the surface of the convex part with the nanodiamond polyimide polishing sheet in the electrostatic chuck device, the convex part did not have any chips or the like, indicating that the ceramic particles were firmly bound together through the metal oxide. It could be confirmed.

[Example 10]
As a paint for forming the ceramic film 16, 6 parts by mass of a toluene solution of yttrium laurate (solid content 10% by mass) is added to 4 parts by mass of spherical magnesia particles (manufactured by Denka, MgO) with an average primary particle diameter of 0.3 μm. An electrostatic chuck device of Example 10 was produced in the same manner as Example 1 except that the additives were used. After polishing the surface of the convex part with the nanodiamond polyimide polishing sheet in the electrostatic chuck device, the convex part did not have any chips or the like, indicating that the ceramic particles were firmly bound together through the metal oxide. It could be confirmed.

[Example 11]
Example 1 except that 2000 parts by mass of yttria particles having an average primary particle diameter of 0.3 μm were mixed and dissolved in an appropriate amount of water based on 100 parts by mass of polyacrylamide resin as the paint for forming the ceramic layer 15. In the same manner as above, an electrostatic chuck device of Example 11 was manufactured.

[Example 12]
In the same manner as in Example 1, except that 2000 parts by mass of alumina particles having an average primary particle diameter of 0.3 μm were mixed with 100 parts by mass of polyimide resin solution as the paint for forming the ceramic layer 15. An electrostatic chuck device of Example 12 was manufactured.

[Example 13]
Example 1 except that 2000 parts by mass of alumina particles having an average primary particle diameter of 0.3 μm were mixed and dissolved in an appropriate amount of solvent to 100 parts by mass of epoxy resin as the paint for forming the ceramic layer 15. In the same manner, an electrostatic chuck device of Example 13 was manufactured.

[Example 14]
Example 1 except that 2000 parts by mass of alumina particles having an average primary particle diameter of 0.3 μm were mixed and dissolved in an appropriate amount of solvent to 100 parts by mass of acrylic resin as the paint for forming the ceramic layer 15. In the same manner, an electrostatic chuck device of Example 14 was manufactured.

[Comparative example 1]
An electrostatic chuck device of Comparative Example 1 was manufactured in the same manner as in Example 1 except that the paint for forming the ceramic film 16 used in Example 1 was used as the paint for forming the ceramic layer 15.

[Checking the ceramic membrane]
The ceramic film 16 formed on the surface of each electrostatic chuck device in Examples 1 to 14 was imaged using a scanning electron microscope (SEM) to confirm the state of each particle. As a result, it was confirmed that in the ceramic film 16 formed on the surface of each electrostatic chuck device in Examples 1 to 14, at least some of the ceramic particles were bound together via metal oxides. Ta.

[evaluation]
Using the electrostatic chuck devices obtained in Examples 1 to 14, the following voltage withstand test was conducted.

<Voltage resistance>
A copper foil was placed on the suction surface of the electrostatic chuck device, and the copper foil and the base were grounded.
Next, a voltage is applied between the terminals provided at both ends of the comb-shaped electrode, and then the applied voltage difference (voltage difference between the terminals) is gradually increased until the applied voltage reaches the point at which dielectric breakdown occurs. The difference was measured.

As a result of evaluating the voltage resistance, the electrostatic chuck devices of Examples 1 to 14 did not cause dielectric breakdown even when the applied voltage difference was 20 kV or more.

Further, using the electrostatic chuck devices obtained in Examples 1 to 14 and Comparative Example 1, the following adhesion test was conducted.
<Adhesion>
A tape peel test was performed on the suction surface of the electrostatic chuck device to evaluate the adhesion. The tape peeling test was carried out in accordance with the "1) Tape test method" of "g) Peeling test method" in JISH8504 (1999) "Plating adhesion test method".
As a result, in the electrostatic chuck devices of Examples 1 to 14, there was no deposit on the adhesive surface of the adhesive tape.
On the other hand, in the electrostatic chuck device of Comparative Example 1, some of the convex portions were attached to the adhesive surface of the adhesive tape.

10 Electrostatic chuck device 11 Base 12 Electrode 13 Ceramic layer 14 Convex portion 15 Ceramic layer 16 Ceramic film 21 Ceramic particles 22 Metal oxide 100, 200 Electrostatic chuck device 110 First adhesive layer 120 First insulating organic film 130 Second adhesive layer 210 Second insulating organic film

Claims (5)

An electrostatic chuck device having a plurality of convex portions on a suction surface,
The convex portion has a ceramic film and a ceramic layer containing a resin binder,
The ceramic film contains ceramic particles and a metal oxide,
An electrostatic chuck device characterized in that at least some of the ceramic particles are bound together via the metal oxide. The electrostatic chuck device according to claim 1, wherein the ceramic particles are at least one selected from the group consisting of alumina, magnesia, yttria, zirconia, silica, and zinc oxide. The electrostatic chuck device according to claim 1 or 2, wherein the average primary particle diameter of the ceramic particles is 0.1 μm or less and 50 μm or less. Claim 1, wherein the metal oxide is a metal oxide obtained by heat-treating the organometallic compound to decompose and remove organic components and oxidizing the metal constituting the organometallic compound. The electrostatic chuck device according to any one of items 3 to 3. 5. The electrostatic chuck device according to claim 4, wherein the metal constituting the organometallic compound is at least one selected from the group consisting of aluminum, yttrium, and magnesium.

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